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Title: Formaldehyde roaming dynamics: Comparison of quasi-classical trajectory calculations and experiments

Abstract

The photodissociation dynamics of roaming in formaldehyde are studied by comparing quasi-classical trajectory calculations performed on a new potential energy surface (PES) to new and detailed experimental results detailing the CO + H2 product state distributions and their correlations. The new PES proves to be a significant improvement over the past one, now more than a decade old. The new experiments probe both the CO and H2 products of the formaldehyde dissociation. The experimental and trajectory data offer unprecedented detail about the correlations between internal states of the CO and H2 dissociation products as well as information on how these distributions are different for the roaming and transition-state pathways. The data investigated include, for dissociation on the formaldehyde 2143 band, the speed distributions for individual vibrational/rotational states of the CO products, providing information about the correlated internal energy distributions of the H2 product, and the rotational and vibrational distributions for the CO and H2 products as well as the contributions to each from both the transition state and roaming channels. The agreement between the trajectory and experimental data is quite satisfactory, although minor differences are noted. In conclusion, the general agreement provides support for future use of the experimental techniquesmore » and the new PES in understanding the dynamics of photodissociative processes.« less

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [2]; ORCiD logo [4];  [5]
  1. Georgia Inst. of Technology, Atlanta, GA (United States); Emory Univ., Atlanta, GA (United States)
  2. Emory Univ., Atlanta, GA (United States)
  3. Emory Univ., Atlanta, GA (United States); Univ. of Heidelberg, Heidelberg (Germany)
  4. The Univ. of New South Wales, Sydney, NSW (Australia); The Univ. of Bristol, Bristol (United Kingdom)
  5. The Univ. of New South Wales, Sydney, NSW (Australia)
Publication Date:
Research Org.:
Emory Univ., Atlanta, GA (United States). Dept. of Chemistry and Cherry L. Emerson Center for Scientific Computation
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1465989
Alternate Identifier(s):
OSTI ID: 1361866
Grant/Contract Number:  
FG02-97ER14782
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 1; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Houston, Paul L., Wang, Xiaohong, Ghosh, Aryya, Bowman, Joel M., Quinn, Mitchell S., and Kable, Scott H. Formaldehyde roaming dynamics: Comparison of quasi-classical trajectory calculations and experiments. United States: N. p., 2017. Web. doi:10.1063/1.4982823.
Houston, Paul L., Wang, Xiaohong, Ghosh, Aryya, Bowman, Joel M., Quinn, Mitchell S., & Kable, Scott H. Formaldehyde roaming dynamics: Comparison of quasi-classical trajectory calculations and experiments. United States. doi:10.1063/1.4982823.
Houston, Paul L., Wang, Xiaohong, Ghosh, Aryya, Bowman, Joel M., Quinn, Mitchell S., and Kable, Scott H. Tue . "Formaldehyde roaming dynamics: Comparison of quasi-classical trajectory calculations and experiments". United States. doi:10.1063/1.4982823. https://www.osti.gov/servlets/purl/1465989.
@article{osti_1465989,
title = {Formaldehyde roaming dynamics: Comparison of quasi-classical trajectory calculations and experiments},
author = {Houston, Paul L. and Wang, Xiaohong and Ghosh, Aryya and Bowman, Joel M. and Quinn, Mitchell S. and Kable, Scott H.},
abstractNote = {The photodissociation dynamics of roaming in formaldehyde are studied by comparing quasi-classical trajectory calculations performed on a new potential energy surface (PES) to new and detailed experimental results detailing the CO + H2 product state distributions and their correlations. The new PES proves to be a significant improvement over the past one, now more than a decade old. The new experiments probe both the CO and H2 products of the formaldehyde dissociation. The experimental and trajectory data offer unprecedented detail about the correlations between internal states of the CO and H2 dissociation products as well as information on how these distributions are different for the roaming and transition-state pathways. The data investigated include, for dissociation on the formaldehyde 2143 band, the speed distributions for individual vibrational/rotational states of the CO products, providing information about the correlated internal energy distributions of the H2 product, and the rotational and vibrational distributions for the CO and H2 products as well as the contributions to each from both the transition state and roaming channels. The agreement between the trajectory and experimental data is quite satisfactory, although minor differences are noted. In conclusion, the general agreement provides support for future use of the experimental techniques and the new PES in understanding the dynamics of photodissociative processes.},
doi = {10.1063/1.4982823},
journal = {Journal of Chemical Physics},
number = 1,
volume = 147,
place = {United States},
year = {2017},
month = {5}
}

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    Dynamics and quantum yields of H 2 + CH 2 CO as a primary photolysis channel in CH 3 CHO
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